CN108855158B - Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst - Google Patents

Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst Download PDF

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CN108855158B
CN108855158B CN201810553030.3A CN201810553030A CN108855158B CN 108855158 B CN108855158 B CN 108855158B CN 201810553030 A CN201810553030 A CN 201810553030A CN 108855158 B CN108855158 B CN 108855158B
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cobalt
ruthenium
catalyst
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heterogeneous catalyst
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CN108855158A (en
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侯震山
贡红辉
李迪帆
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East China University of Science and Technology
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    • B01J35/393—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
    • B01J35/615—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation

Abstract

The invention discloses a preparation method of a cobalt-ruthenium bimetallic heterogeneous catalyst, which comprises the following steps: dissolving a cobalt precursor in water to prepare a solution, adding zirconium phosphate, stirring for reaction, drying, adding the obtained substance into an aqueous solution containing a ruthenium compound, stirring for reaction, drying, roasting, grinding and screening to obtain the cobalt-ruthenium bimetallic heterogeneous catalyst. The cobalt-ruthenium bimetallic heterogeneous catalyst provided by the invention is a catalyst for preparing propionaldehyde by hydrogenolysis of glycerol, which can react in a continuous fixed bed and has high catalytic activity, high selectivity and good stability.

Description

Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a cobalt-ruthenium bimetallic heterogeneous catalyst.
Background
Traditional non-renewable fossil energy sources are increasingly unable to meet the growing energy needs of humans, and therefore, there is a need for an alternative resource that can meet energy needs and is renewable. This demand has led to the emergence of biodiesel, which is receiving attention for its environmental protection, safety and renewability, and is considered as a new energy source that can replace petroleum diesel. Various studies conducted to date have shown that the use of biodiesel can reduce the emissions of typical pollutants such as particulate matter, carbon monoxide, nitrogen oxides, sulfides, polycyclic aromatic hydrocarbons and monocyclic aromatic compounds. This is because the ideal biodiesel has high oxygen content, low sulfur content and low aromatic hydrocarbon content, and is biodegradable. Biodiesel is obtained from renewable resources like fatty acid alkyl esters of palm, rapeseed, soy. There are many methods for producing biodiesel, but a method of general choice is to produce biodiesel from fats and oils and alcohols through transesterification, in which a large amount of glycerin, which is a by-product, is produced, and about 1 kg of glycerin is produced per 10 kg of biodiesel produced. Along with the improvement of the biodiesel productivity, the market supply of the glycerol is continuously expanded, the high-end market has high requirement on the purity of the glycerol, the purification is not economical, but the value of crude glycerol is not high. The excess glycerin not only brings serious treatment problems, but also affects the economy of the biodiesel industry. Due to the multifunctional structure and the performance of glycerol, various high-value-added chemicals such as propanol, acrolein, 1, 2-propylene glycol, 1, 3-propylene glycol, propionaldehyde, lactic acid and the like can be prepared from different reaction paths. Therefore, it is a pending and significant topic to open a new way of comprehensive utilization of glycerol, i.e. a sustainable route for preparing chemicals from biomass. Propionaldehyde is an important chemical product and chemical raw material, and has wide application in rubber, plastics, paint, medicine, in particular to pesticide, feed and the like. Propionaldehyde is subjected to atmospheric pressure oxidation reaction to produce propionic acid, which is an important fine chemical and an important intermediate for producing other fine chemicals, and has wide application. Propionaldehyde is subjected to hydrogenation reaction in the presence of a skeletal nickel catalyst to prepare n-propanol, the n-propanol is used for producing probenecid, sodium valproate, erythromycin, epileptic healthy and safe adhesive hemostats, prothiochiamine, dipropyl phthalate vinegar and the like in an aqueous solution in the pharmaceutical industry, and the n-propanol is used for synthesizing various kinds of vinegar and is used for many aspects such as food additives, plasticizers, spices and the like; the n-propanol derivatives, especially di-n-propylamine, have many applications in the production of medicines and pesticides, and are used for producing pesticides sulfamethoxazole, dimethachlor, isoprotulin, sweepin, sulindac, flurazole and the like. The current industrial synthesis method of propionaldehyde mainly comprises the following steps: 1. propanol oxidation method: propyl alcohol, potassium dichromate and dilute sulfuric acid are used as raw materials and react at the temperature of 60 ℃ to prepare propionaldehyde; 2. propylene oxide isomerization process: propylene oxide is adopted as a raw material, chromium vanadium is adopted as a catalyst, crude propionaldehyde is prepared by reaction at the temperature of 200-210 ℃, and then a propionaldehyde product is obtained by refining through a rectifying tower; 3. acrolein hydrogenation method: the acrolein hydrogenation method is that nickel oxide or nickel carbonate, sulfide or sulfur (the sulfur content is 30 percent of the nickel content), diatomite, water glass and zeolite are reduced by hydrogen at the temperature of 100-150 ℃ to prepare a catalyst, and then under the condition that the temperature is 210 ℃, acrolein and hydrogen react through the catalyst to prepare propionaldehyde. The most basic raw material acrolein can be prepared by oxidizing propylene at 350 ℃ and higher pressure by using cuprous oxide as a catalyst; 4. a byproduct method: propylene is used as a raw material, and is oxidized by air under the action of catalysts of copper chloride and lead chloride, so that a main product of acetone and a byproduct of propionaldehyde are generated. 5. Oxo synthesis: the ethylene hydroformylation process with ethylene, carbon monoxide and hydrogen as material and cobalt and rhodium-phosphine complex as catalyst has reaction temperature of 100 deg.c and pressure of 1.27-1.47MPa to produce propionaldehyde in 94% selectivity. All of these processes use petroleum as the starting material. Obviously, the development of alternative petroleum resources for preparing propanol is very promising. The method for preparing propionaldehyde by hydrogenolysis of glycerol is a sustainable approach based on biomass utilization, and the approach is developed, so that the production cost of biodiesel can be reduced, the comprehensive economic benefit can be improved, the problem of excess glycerol can be solved, and the chemical product with higher added value can be prepared. To date, the study of hydrogenolysis of glycerol is still in the beginning and further exploration is needed to find better catalysts and processes. The method fully utilizes the byproduct crude glycerine generated in the biodiesel preparation process to catalyze and prepare various chemicals with high added values, can improve the comprehensive utilization rate of resources, can extend the biodiesel industry chain, improves the overall competitiveness of the biodiesel green industry, and has wide application prospect.
In view of the above, there is a need to provide a catalyst for preparing propionaldehyde by hydrogenolysis of glycerol, which has good catalytic performance, low cost and simple preparation method.
Disclosure of Invention
The invention aims to provide a preparation method of a cobalt-ruthenium bimetallic heterogeneous catalyst for preparing propionaldehyde by glycerol hydrogenolysis, which has good catalytic performance and simple preparation method.
It is another object of the present invention to provide a cobalt-ruthenium bimetallic heterogeneous catalyst prepared by the process.
It is a further object of the present invention to provide a use of the cobalt-ruthenium bimetallic heterogeneous catalyst prepared by the method for preparing propionaldehyde by hydrogenolysis of glycerol.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing a cobalt-ruthenium bimetallic heterogeneous catalyst, comprising the steps of:
dissolving a cobalt precursor in water to prepare a solution, adding zirconium phosphate, stirring for reaction, drying, adding the obtained substance into an aqueous solution containing a ruthenium compound, stirring for reaction, drying, roasting, grinding and screening to obtain the cobalt-ruthenium bimetallic heterogeneous catalyst.
The precursor of the cobalt is at least one of cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt acetate and cobalt carbonate.
The ruthenium-containing compound is ruthenium trichloride hydrate.
The concentration of the solution prepared by dissolving the cobalt precursor in water is 1-15%.
The concentration of the aqueous solution of the ruthenium compound is 1-10%.
The stirring reaction is carried out at room temperature for 1-24 h.
The drying temperature is 80-150 ℃, and the drying time is 1-24 hours.
The roasting temperature is 300-500 ℃, and the roasting time is 1-24 hours.
And the grinding and screening are carried out by passing through a standard molecular sieve of 20-40 meshes.
The mass ratio of the zirconium phosphate to the cobalt precursor is 1 (0.05-0.5), and preferably 1 (0.05-0.3).
The mass ratio of the ruthenium-containing compound to the cobalt precursor is 1 (1-6), and preferably 2: 3.
The preparation method of the zirconium phosphate comprises the following steps:
adding dropwise an aqueous solution of ammonium dihydrogen phosphate to an aqueous solution of zirconium oxychloride, vigorously stirring, and stirring the resulting mixture at room temperature overnightThen suction filtering, washing with deionized water until the pH value of the filtrate is 6, and checking with silver nitrate solution for no Cl-The white precipitate was then dried and the resulting powder was calcined to obtain the zirconium phosphate.
The molar ratio of the ammonium dihydrogen phosphate to the zirconium oxychloride is (1-3) to 1, and preferably 2 to 1.
The concentrations of the ammonium dihydrogen phosphate aqueous solution and the zirconium oxychloride aqueous solution are both 0.5-1.5 mol/L, and preferably 1 mol/L.
Drying the white precipitate at the temperature of 100-150 ℃ for 1-24 h;
the powder roasting temperature is 350-450 ℃, and the time is 1-24 hours.
The invention also provides a cobalt-ruthenium bimetallic heterogeneous catalyst prepared by the method, which takes zirconium phosphate as a carrier, the Co loading capacity is 2-6 wt%, the Ru loading capacity is 1-2 wt%, the particle size is 20-40 meshes, and the specific surface area is 100-200 m2/g。
In another aspect, the invention provides a use of the cobalt-ruthenium bimetallic heterogeneous catalyst prepared by the method for preparing propionaldehyde by hydrogenolysis of glycerol.
The use comprises the following steps: placing the cobalt-ruthenium bimetallic heterogeneous catalyst in the middle of a continuous flow fixed bed reactor, reducing the cobalt-ruthenium bimetallic heterogeneous catalyst for at least 0.5h under a nitrogen-hydrogen mixed gas at the temperature of 210-330 ℃ before reaction, pumping a glycerol aqueous solution into the reactor for reaction, and sampling and analyzing after cooling.
The reaction temperature of the reaction system in the reactor is 210-330 ℃.
The concentration of the glycerol aqueous solution is at least 5%, and the flow rate is at least 0.04 ml/min.
The sampling analysis is carried out after the reaction time is at least 10h, and the glycerol conversion rate and the propionaldehyde selectivity are detected and analyzed by gas chromatography.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the cobalt-ruthenium bimetallic heterogeneous catalyst provided by the invention is a catalyst for preparing propionaldehyde by hydrogenolysis of glycerol, which can react in a continuous fixed bed and has high catalytic activity, high selectivity and good stability.
The cobalt-ruthenium bimetallic heterogeneous catalyst provided by the invention adopts a distributed impregnation method to load cobalt and ruthenium on zirconium phosphate, wherein the load of Co is 2-6 wt%, and the load of Ru is 1-3 wt%.
The cobalt-ruthenium bimetallic heterogeneous catalyst provided by the invention has high catalyst activity and selectivity and better catalytic stability, and after the continuous fixed bed reaction is carried out for 50 hours, the selectivity of propanol is still kept above 80%, so that the cobalt-ruthenium bimetallic heterogeneous catalyst is a superior catalyst system for the reaction for preparing propionaldehyde by glycerol hydrogenolysis.
Drawings
FIG. 1 is a schematic flow diagram of a cobalt-ruthenium bimetallic heterogeneous catalyst prepared by an example of the present invention for the preparation of propionaldehyde by the hydrogenolysis of glycerol.
Wherein: 1 is a hydrogen cylinder; 2 is a device for holding 10 wt% aqueous glycerol solution; 3 is a high-pressure liquid phase pump; 4 is a catalyst; 5 is a reaction tube; 6 is a condenser pipe; 7 is a back pressure valve; 8 is a low-temperature cooling system; 9 is a three-stage absorption device; s1 is a high-pressure reducing valve; v1 is a first check valve; v2 is a second one-way valve; v3 is a third check valve.
Figure 2 is the effect of reaction temperature on glycerol hydrogenolysis with different temperatures on the abscissa, 210 ℃ (example 1), 230 ℃ (example 2), 250 ℃ (example 3), 270 ℃ (example 4), 290 ℃ (example 5), in which: (■) glycerol conversion, (●) propanal selectivity, (-a) acrolein selectivity, (-a) propanol selectivity, (-a) hydroxyacetone selectivity. As can be seen from fig. 2, the selectivity to propionaldehyde is highest, reaching 81%, when the reaction temperature is 270 ℃.
FIG. 3 is a Scanning Electron Micrograph (SEM), FIG. 3a is a SEM of the Co-Ru/ZrP catalyst of example 1, FIG. 3b is a SEM of the Co-Ru/ZrP catalyst of example 2, FIG. 3c is a SEM of the Co-Ru/ZrP catalyst of example 3, FIG. 3d is a SEM of the Co-Ru/ZrP catalyst of example 4, FIG. 3e is a SEM of the Co-Ru/ZrP catalyst of example 5, and it can be seen from the SEM shown in FIG. 3 that the morphology of the catalyst does not change significantly and thus the morphology of the catalyst does not change after loading the Ru-Co metal.
FIG. 4 is a Transmission Electron Micrograph (TEM) in which a and b in FIG. 4 represent transmission electron micrographs of Co-Ru/ZrP catalysts of example 4 in different sizes.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The reagents and starting materials used in the present invention are commercially available or can be prepared according to literature procedures. Unless otherwise indicated, percentages and parts are by weight.
Example 1
Ammonium dihydrogen phosphate (NH)4H2PO4) Adding aqueous solution (1.0mol/L, 64ml) into aqueous solution of zirconium oxychloride (1.0mol/L, 32ml) dropwise, wherein the molar ratio of ammonium dihydrogen phosphate to zirconium oxychloride is 2:1, stirring at room temperature overnight, suction-filtering, washing with deionized water until the pH value of filtrate is 6, and checking with silver nitrate solution for no Cl-1Until then, the white precipitate was dried at 100 ℃ for 12 hours, and the zirconium phosphate obtained by drying was calcined in a muffle furnace at 450 ℃ for 4 hours and ground into powder with a mortar to obtain zirconium phosphate.
Weighing 0.098g of cobalt nitrate hexahydrate, dissolving the cobalt nitrate hexahydrate in 1.2ml of water, weighing 1g of the obtained zirconium phosphate, adding the zirconium phosphate into the solution, stirring the solution at 40 ℃ for 24 hours, and drying the solution at 100 ℃ for 12 hours to obtain a catalyst named as Co/ZrP, wherein the Co loading capacity is 2%; weighing 0.053g of ruthenium trichloride trihydrate, dissolving the ruthenium trichloride trihydrate into 1.2ml of water, weighing 1g of Co/ZrP, adding the Co/ZrP into the solution, stirring for 24 hours, drying for 12 hours at 100 ℃, roasting the dried catalyst in a muffle furnace at 300 ℃ for 4 hours, grinding the catalyst into powder by using a mortar, sieving the powder by using a standard sieve of 20-40 meshes, and naming the obtained cobalt-ruthenium bimetal heterogeneous catalyst as Co-Ru/ZrP, wherein the Ru loading is 2%, and the specific surface area is 156m2/g。
As shown in fig. 1, fig. 1 is a schematic flow diagram of a cobalt-ruthenium bimetallic heterogeneous catalyst prepared by the embodiment of the invention for preparing propionaldehyde by the hydrogenolysis of glycerol; the cobalt-ruthenium bimetallic heterogeneous catalyst (Co-Ru/ZrP catalyst) (with the particle size of 20-40 meshes), namely the catalyst 4, is placed in the middle of a continuous flow fixed bed reactor, a reaction tube 5 is a stainless steel tube, and two ends of a bed layer are fixed by quartz wool and quartz sand and used for supporting the catalyst 4 and playing roles in preheating and vaporizing raw materials. The reaction temperature is controlled by a thermocouple arranged in the middle of the catalyst bed layer; before the reaction, the catalyst 4 is reduced for 1h under the nitrogen-hydrogen mixed gas at the temperature of 220-330 ℃; hydrogen is input into a reaction tube 5 from a hydrogen cylinder 1 through a high-pressure reducing valve S1 and a first one-way valve V1, then, a 10 wt% glycerol aqueous solution is pumped into a reactor through a high-pressure liquid phase pump 3 and a second one-way valve V2 from a device 2 containing the 10 wt% glycerol aqueous solution (the pressure of a reaction system is controlled through a back pressure valve 7), the flow rate of the glycerol solution is 0.04ml/min, the reaction temperature is 210 ℃, the reaction pressure is 2MPa, a reaction product is cooled through a condensing tube 6, is cooled through a low-temperature cooling system 8, is collected in the condensing tube through a three-stage absorption device 9, is collected once every two hours, and is analyzed in an off-line manner; the other end of the condensation pipe 6 is connected with a third one-way valve V3, and some substances which have stronger volatility and are not condensed can be lost along with the carrier gas nitrogen, so that the tail gas is absorbed by ethyl acetate through a three-stage absorption device 9 to avoid product loss. After 15-18h, sampling and detecting and analyzing by gas chromatography, wherein the conversion rate of the glycerol is 100%, the selectivity of the propionaldehyde is 65%, after 50h, the glycerol is completely converted, and the selectivity of the propionaldehyde still reaches 60%.
Example 2
Ammonium dihydrogen phosphate (NH)4H2PO4) Adding aqueous solution (1.0mol/L, 64ml) into aqueous solution of zirconium oxychloride (1.0mol/L, 32ml) dropwise, wherein the molar ratio of ammonium dihydrogen phosphate to zirconium oxychloride is 2:1, stirring at room temperature overnight, suction-filtering, washing with deionized water until the pH value of filtrate is 6, and checking with silver nitrate solution for no Cl-1Until then, the white precipitate was dried at 100 ℃ for 12 hours, and the dried zirconium phosphate was calcined in a muffle furnace at 350 ℃ for 4 hours and pulverized with a mortar to obtain zirconium phosphate.
0.147g of cobalt nitrate hexahydrate is weighed out and dissolved1.2ml of water, then weighing 1g of the obtained zirconium phosphate, adding the zirconium phosphate into the solution, stirring the solution at 40 ℃ for 24 hours, and drying the solution at 100 ℃ for 12 hours to obtain a catalyst named as Co/ZrP, wherein the Co loading capacity is 3%; weighing 0.053g of ruthenium trichloride trihydrate, dissolving the ruthenium trichloride trihydrate into 1.2ml of water, weighing 1g of Co/ZrP, adding the Co/ZrP into the solution, stirring for 24 hours, drying for 12 hours at 100 ℃, roasting the dried catalyst in a muffle furnace at 400 ℃ for 4 hours, grinding the catalyst into powder by using a mortar, sieving the powder by using a standard sieve of 20-40 meshes, and naming the obtained cobalt-ruthenium bimetal heterogeneous catalyst as Co-Ru/ZrP, wherein the Ru loading is 2%, and the specific surface area is 130m2/g。
The cobalt-ruthenium bimetallic heterogeneous catalyst (Co-Ru/ZrP catalyst) (the particle size is 20-40 meshes of a standard sieve) is placed in the middle of a continuous flow fixed bed reactor, a reaction tube is a stainless steel tube, and two ends of a bed layer are fixed by quartz wool and quartz sand to support the catalyst and play a role in preheating and vaporizing raw materials. The reaction temperature is controlled by a thermocouple arranged in the middle of the catalyst bed layer; before the reaction, the catalyst is reduced for 1h under the nitrogen-hydrogen mixed gas at the temperature of 220-330 ℃; hydrogen is input into a reaction tube from a hydrogen bottle through a high-pressure reducing valve and a first one-way valve, then, a 10 wt% glycerol aqueous solution is pumped into a reactor from a device containing the 10 wt% glycerol aqueous solution through a high-pressure liquid phase pump and a second one-way valve (the pressure of a reaction system is controlled through a backpressure valve), the flow rate of the glycerol solution is 0.04ml/min, the reaction temperature is 230 ℃, the reaction pressure is 2MPa, a reaction product is cooled through a condensing tube, cooled through a low-temperature cooling system, collected in a condensing tank through a three-stage absorption device, collected once every two hours and analyzed off line; the other end of the condensation pipe is connected with a third one-way valve, and some substances which have stronger volatility and are not condensed can be lost along with the nitrogen gas as the carrier gas, so that the tail gas is absorbed by ethyl acetate through a three-stage absorption device to avoid product loss. After 16-18h, sampling and detecting and analyzing by gas chromatography, wherein the conversion rate of the glycerol is 100%, the selectivity of the propionaldehyde is 73%, after 50h, the glycerol is completely converted, and the selectivity of the propionaldehyde still reaches 70%.
Example 3
Ammonium dihydrogen phosphate (NH)4H2PO4) Adding aqueous solution (1.0mol/L, 64ml) into aqueous solution of zirconium oxychloride (1.0mol/L, 32ml) dropwise, wherein the molar ratio of ammonium dihydrogen phosphate to zirconium oxychloride is 2:1, stirring at room temperature overnight, suction-filtering, washing with deionized water until the pH value of filtrate is 6, and checking with silver nitrate solution for no Cl-1The white precipitate was then dried at 100 ℃ for 12 hours, and the dried zirconium phosphate was calcined in a muffle furnace at 400 ℃ for 4 hours and ground into powder with a mortar to obtain zirconium phosphate.
Weighing 0.196g of cobalt nitrate hexahydrate, dissolving the cobalt nitrate hexahydrate in 1.2ml of water, weighing 1g of the obtained zirconium phosphate, adding the zirconium phosphate into the solution, stirring the solution at 40 ℃ for 24 hours, and drying the solution at 100 ℃ for 12 hours to obtain a catalyst named as Co/ZrP, wherein the Co loading capacity is 4%; weighing 0.053g of ruthenium trichloride trihydrate, dissolving the ruthenium trichloride trihydrate into 1.2ml of water, weighing 1g of Co/ZrP, adding the Co/ZrP into the solution, stirring for 24 hours, drying for 12 hours at 100 ℃, roasting the dried catalyst in a muffle furnace at 400 ℃ for 4 hours, grinding the catalyst into powder by using a mortar, sieving the powder by using a standard sieve of 20-40 meshes, and naming the obtained cobalt-ruthenium bimetal heterogeneous catalyst as Co-Ru/ZrP, wherein the Ru loading is 2%, and the specific surface area is 115m2/g。
The cobalt-ruthenium bimetallic heterogeneous catalyst (Co-Ru/ZrP catalyst) (the particle size is 20-40 meshes of a standard sieve) is placed in the middle of a continuous flow fixed bed reactor, a reaction tube is a stainless steel tube, and two ends of a bed layer are fixed by quartz wool and quartz sand to support the catalyst and play a role in preheating and vaporizing raw materials. The reaction temperature is controlled by a thermocouple arranged in the middle of the catalyst bed layer; before the reaction, the catalyst is reduced for 1h under the nitrogen-hydrogen mixed gas at the temperature of 220-330 ℃; hydrogen is input into a reaction tube from a hydrogen bottle through a high-pressure reducing valve and a first one-way valve, then, a 10 wt% glycerol aqueous solution is pumped into a reactor from a device containing the 10 wt% glycerol aqueous solution through a high-pressure liquid phase pump and a second one-way valve (the pressure of a reaction system is controlled through a backpressure valve), the flow rate of the glycerol solution is 0.04ml/min, the reaction temperature is 250 ℃, the reaction pressure is 2MPa, a reaction product is cooled through a condensing tube, cooled through a low-temperature cooling system, collected in a condensing tank through a three-stage absorption device, collected once every two hours and analyzed off line; the other end of the condensation pipe is connected with a third one-way valve, and some substances which have stronger volatility and are not condensed can be lost along with the nitrogen gas as the carrier gas, so that the tail gas is absorbed by ethyl acetate through a three-stage absorption device to avoid product loss. After 15-18h, sampling and detecting and analyzing by gas chromatography, wherein the conversion rate of the glycerol is 100%, the selectivity of the propionaldehyde is 77%, after 50h, the glycerol is completely converted, and the selectivity of the propionaldehyde is still 75%.
Example 4
Ammonium dihydrogen phosphate (NH)4H2PO4) Adding aqueous solution (1.0mol/L, 64ml) into aqueous solution of zirconium oxychloride (1.0mol/L, 32ml) dropwise, wherein the molar ratio of ammonium dihydrogen phosphate to zirconium oxychloride is 2:1, stirring at room temperature overnight, suction-filtering, washing with deionized water until the pH value of filtrate is 6, and checking with silver nitrate solution for no Cl-1The white precipitate was then dried at 100 ℃ for 12 hours, and the dried zirconium phosphate was calcined in a muffle furnace at 400 ℃ for 4 hours and ground into powder with a mortar to obtain zirconium phosphate.
Weighing 0.245g of cobalt nitrate hexahydrate, dissolving the cobalt nitrate hexahydrate in 1.2ml of water, weighing 1g of the obtained zirconium phosphate, adding the zirconium phosphate into the solution, stirring the solution at 40 ℃ for 24 hours, and drying the solution at 100 ℃ for 12 hours to obtain a catalyst named as Co/ZrP, wherein the Co loading capacity is 5%; weighing 0.053g of ruthenium trichloride trihydrate, dissolving the ruthenium trichloride trihydrate into 1.2ml of water, weighing 1g of Co/ZrP, adding the Co/ZrP into the solution, stirring for 24 hours, drying for 12 hours at 100 ℃, roasting the dried catalyst in a muffle furnace at 400 ℃ for 4 hours, grinding the catalyst into powder by using a mortar, sieving the powder by using a standard sieve of 20-40 meshes, and naming the obtained cobalt-ruthenium bimetal heterogeneous catalyst as Co-Ru/ZrP, wherein the Ru loading is 2%, and the specific surface area is 101m2/g。
The cobalt-ruthenium bimetallic heterogeneous catalyst (Co-Ru/ZrP catalyst) (the particle size is 20-40 meshes of a standard sieve) is placed in the middle of a continuous flow fixed bed reactor, a reaction tube is a stainless steel tube, and two ends of a bed layer are fixed by quartz wool and quartz sand to support the catalyst and play a role in preheating and vaporizing raw materials. The reaction temperature is controlled by a thermocouple arranged in the middle of the catalyst bed layer; before the reaction, the catalyst is reduced for 1h under the nitrogen-hydrogen mixed gas at the temperature of 220-330 ℃; hydrogen is input into a reaction tube from a hydrogen bottle through a high-pressure reducing valve and a first one-way valve, then, a 10 wt% glycerol aqueous solution is pumped into a reactor from a device containing the 10 wt% glycerol aqueous solution through a high-pressure liquid phase pump and a second one-way valve (the pressure of a reaction system is controlled through a backpressure valve), the flow rate of the glycerol solution is 0.04ml/min, the reaction temperature is 270 ℃, the reaction pressure is 2MPa, a reaction product is cooled through a condensing tube, cooled through a low-temperature cooling system, collected in a condensing tank through a three-stage absorption device, collected once every two hours and analyzed off line; the other end of the condensation pipe is connected with a third one-way valve, and some substances which have stronger volatility and are not condensed can be lost along with the nitrogen gas as the carrier gas, so that the tail gas is absorbed by ethyl acetate through a three-stage absorption device to avoid product loss. After 15-18h, sampling and detecting and analyzing by gas chromatography, wherein the conversion rate of the glycerol is 100%, the selectivity of the propionaldehyde is 81%, after 50h, the glycerol is completely converted, and the selectivity of the propionaldehyde still reaches 80%.
Example 5
Ammonium dihydrogen phosphate (NH)4H2PO4) Adding aqueous solution (1.0mol/L, 64ml) into aqueous solution of zirconium oxychloride (1.0mol/L, 32ml) dropwise, wherein the molar ratio of ammonium dihydrogen phosphate to zirconium oxychloride is 2:1, stirring at room temperature overnight, suction-filtering, washing with deionized water until the pH value of filtrate is 6, and checking with silver nitrate solution for no Cl-1The white precipitate was then dried at 100 ℃ for 12 hours, and the dried zirconium phosphate was calcined in a muffle furnace at 400 ℃ for 4 hours and ground into powder with a mortar to obtain zirconium phosphate.
Weighing 0.294g of cobalt nitrate hexahydrate, dissolving the cobalt nitrate hexahydrate in 1.2ml of water, weighing 1g of the obtained zirconium phosphate, adding the zirconium phosphate into the solution, stirring the solution at 40 ℃ for 24 hours, and drying the solution at 100 ℃ for 12 hours to obtain a catalyst named as Co/ZrP, wherein the Co loading capacity is 6%; weighing 0.053g of ruthenium trichloride trihydrate, dissolving the ruthenium trichloride trihydrate into 1.2ml of water, weighing 1g of Co/ZrP, adding the Co/ZrP into the solution, stirring for 24 hours, drying for 12 hours at 100 ℃, roasting the dried catalyst in a muffle furnace at 400 ℃ for 4 hours, grinding the catalyst into powder by using a mortar, sieving the powder by using a standard sieve of 20-40 meshes, and naming the obtained cobalt-ruthenium bimetal heterogeneous catalyst as Co-Ru/ZrP, wherein the Ru loading is 2%, and the specific surface area is 96m2/g。
The cobalt-ruthenium bimetallic heterogeneous catalyst (Co-Ru/ZrP catalyst) (the particle size is 20-40 meshes of a standard sieve) is placed in the middle of a continuous flow fixed bed reactor, a reaction tube is a stainless steel tube, and two ends of a bed layer are fixed by quartz wool and quartz sand to support the catalyst and play a role in preheating and vaporizing raw materials. The reaction temperature is controlled by a thermocouple arranged in the middle of the catalyst bed layer; before the reaction, the catalyst is reduced for 1h under the nitrogen-hydrogen mixed gas at the temperature of 220-330 ℃; hydrogen is input into a reaction tube from a hydrogen bottle through a high-pressure reducing valve and a first one-way valve, then, a 10 wt% glycerol aqueous solution is pumped into a reactor from a device containing the 10 wt% glycerol aqueous solution through a high-pressure liquid phase pump and a second one-way valve (the pressure of a reaction system is controlled through a backpressure valve), the flow rate of the glycerol solution is 0.04ml/min, the reaction temperature is 290 ℃, the reaction pressure is 2MPa, a reaction product is cooled through a condensing tube, cooled through a low-temperature cooling system, collected in a condensing tank through a three-stage absorption device, collected once every two hours and analyzed off line; the other end of the condensation pipe is connected with a third one-way valve, and some substances which have stronger volatility and are not condensed can be lost along with the nitrogen gas as the carrier gas, so that the tail gas is absorbed by ethyl acetate through a three-stage absorption device to avoid product loss. After 15-18h, sampling and detecting and analyzing by gas chromatography, wherein the conversion rate of the glycerol is 100%, the selectivity of the propionaldehyde is 75%, after 50h, the glycerol is completely converted, and the selectivity of the propionaldehyde is still 75%.
Figure 2 is the effect of reaction temperature on glycerol hydrogenolysis with different temperatures on the abscissa, 210 ℃ (example 1), 230 ℃ (example 2), 250 ℃ (example 3), 270 ℃ (example 4), 290 ℃ (example 5), in which: (■) glycerol conversion, (●) propanal selectivity, (-a) acrolein selectivity, (-a) propanol selectivity, (-a) hydroxyacetone selectivity. As can be seen from fig. 2, the selectivity to propionaldehyde is highest, reaching 81%, when the reaction temperature is 270 ℃.
FIG. 3 is a Scanning Electron Micrograph (SEM), FIG. 3a is a SEM of the Co-Ru/ZrP catalyst of example 1, FIG. 3b is a SEM of the Co-Ru/ZrP catalyst of example 2, FIG. 3c is a SEM of the Co-Ru/ZrP catalyst of example 3, FIG. 3d is a SEM of the Co-Ru/ZrP catalyst of example 4, FIG. 3e is a SEM of the Co-Ru/ZrP catalyst of example 5, and it can be seen from the SEM shown in FIG. 3 that the morphology of the catalyst does not change significantly and thus the morphology of the catalyst does not change after loading the Ru-Co metal.
FIG. 4 is a Transmission Electron Micrograph (TEM) in which a and b in FIG. 4 represent transmission electron micrographs of Co-Ru/ZrP catalysts of example 4 in different sizes.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (5)

1. A cobalt-ruthenium bimetallic heterogeneous catalyst for the reaction of preparing propionaldehyde by hydrogenolysis of glycerol is characterized in that the cobalt-ruthenium bimetallic heterogeneous catalyst is prepared by a preparation method comprising the following steps:
(1) dissolving a cobalt precursor in water to prepare a solution, adding zirconium phosphate, stirring for 1-24 hours at room temperature, and drying to obtain an intermediate;
(2) adding the intermediate obtained in the step (1) into an aqueous solution containing a ruthenium compound, stirring for 1-24 hours at room temperature, and drying, roasting, grinding and screening sequentially to obtain a target;
wherein the mass ratio of the zirconium phosphate to the cobalt precursor is 1 (0.05-0.5); the mass ratio of the ruthenium-containing compound to the cobalt precursor is 1 (1-6);
the precursor of cobalt is selected from: at least one of cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt acetate or cobalt carbonate; the ruthenium-containing compound is ruthenium trichloride hydrate;
the target is zirconium phosphate as a carrier, the cobalt loading is 2-6 wt%, and the ruthenium loading is 1-2 wt%;
the particle diameter of the target is 20-40 meshes, and the specific surface area is 100m2/g～200m2/g。
2. The cobalt-ruthenium bi-metal heterogeneous catalyst according to claim 1, wherein the drying temperature in steps (1) and (2) is 80 ℃ to 150 ℃ and the drying time is 1h to 24 h; the roasting temperature is 300-500 ℃, and the roasting time is 1-24 h.
3. The cobalt-ruthenium bi-metal heterogeneous catalyst according to claim 2, wherein the zirconium phosphate used is prepared by a preparation method comprising the following steps:
dropwise adding the aqueous solution of ammonium dihydrogen phosphate into the aqueous solution of zirconium oxychloride, vigorously stirring, stirring the obtained mixture at room temperature overnight, suction-filtering, washing with deionized water until the pH value of the filtrate is 6, and checking with silver nitrate solution for no Cl-Drying the white precipitate, and roasting the obtained powder to obtain the target zirconium phosphate;
wherein the molar ratio of the ammonium dihydrogen phosphate to the zirconium oxychloride is (1-3) to 1.
4. The cobalt-ruthenium bi-metal heterogeneous catalyst according to claim 3, wherein the temperature for drying the white precipitate is 100 ℃ to 150 ℃ for 1h to 24 h; the roasting temperature of the powder is 350-450 ℃, and the roasting time is 1-24 h.
5. The use of a cobalt-ruthenium bimetallic heterogeneous catalyst as defined in any one of claims 1 to 4 as a catalyst for the reaction of hydrogenolysis of glycerol to propionaldehyde;
wherein the reaction temperature of the reaction for preparing the propionaldehyde by the hydrogenolysis of the glycerol is 250-290 ℃.
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